ALTEREGO

Alternative Energy Forms for Green Chemistry

1

• EU-FP7-THEME [NMP.2012.3.0-1] • Highly efficient chemical syntheses using

alternative energy forms

• Alternative Energy Forms for Green Chemistry • Grant agreement no: 309874 • Project duration: 01/01/2013-30/06/2016

ALTEREGO

Objectives and approach

3

INTEGRATION

INTENSIFICATIO

N

ALTERNATIVE ENERGIES

Ultrasound

Microwaves Plasma

INTENSIFIED REACTORS

Mesoscale Tubular Reactors

Micro- and Millireactors

Oscillatory Flow Reactors

Reactive Distillation

INDUSTRIAL APPLICATIONS

Methanol synthesis from CO2

DEC and EMC synthesis with reactive distillation

Paracetamol and APIs crystallization

Advanced Advanced Pharmaceuticals Pharmaceuticals

SynthesisSynthesis

Green Fuel and Green Fuel and Chemicals SynthesisChemicals Synthesis

INTEGRATION

INTENSIFICATIO

N

ALTERNATIVE ENERGIES

Ultrasound

Microwaves Plasma

INTENSIFIED REACTORS

Mesoscale Tubular Reactors

Micro- and Millireactors

Oscillatory Flow Reactors

Reactive Distillation

INDUSTRIAL APPLICATIONS

Methanol synthesis from CO2

DEC and EMC synthesis with reactive distillation

Paracetamol and APIs crystallization

Advanced Advanced Pharmaceuticals Pharmaceuticals

SynthesisSynthesis

Green Fuel and Green Fuel and Chemicals SynthesisChemicals Synthesis

TU Delft (coordinator): Andrzej Stankiewicz KU Leuven: Tom Van Gerven, Georgios Stefanidis TU Dortmund: Andrzej Gorak, Dorota Pawlucka University of York: Duncan Macquarrie Smart Material: Jan Kunzmann SAIREM: Marilena Radoiu Janssen Pharmaceutica: Peter Van Broeck Akzo Nobel: Tony Kiss, Riaan Schmul

Consortium U

nive

rsiti

es

Tech

Su

ppl

End

user

s

To develop processes activated by alternative energies in the fields of fuels synthesis and pharmaceuticals synthesis Reverse Water-Gas Shift and biomass gasification activated by (microwave) plasma Ethyl methyl carbonate (EMC) and Diethyl Carbonate (DEC) from methanol via

reactive distillation activated by microwaves and ultrasound API synthesis - demethylation of 3-methoxybenzylammonium bromide - activated

by microwaves Paracetamol production in millireactors (cooling crystallization) assisted by

ultrasound Reactive extraction of p-nitrophenolate in microreactors assisted by ultrasound Enzymatic reactive distillation to produce butylbutyrate with ultrasound

General aim

Appl

icat

ion

area

s

TUDO TUD

YORK SAIREM

JP

JP KUL TUD

SAIREM

AN TUDO TUD

SAIREM SM

Advanced pharmaceutical synthesis

Green fuel synthesis

Technologies

Dem

onstration

WP 1 WP 3 WP 2

WP 5

WP 4

KUL TUD

TUDO JP

SM

TUD AN

SAIREM

Data generation Mechanisms and models

Equipment design and scale up

General Work Plan

Ultra-sound

Micro-waves

Plasma

Expected impact

• Technological Application of ultrasound, microwaves and plasma to

smartly use long known capabilities: to boost the selectivity, conversions and speed of reaction and separation Enable widespread application via development of

technological know-how on efficient reactor & process design & optimization: discovery and description of the mechanisms involved in the effects of the external fields on the reactions, mass transfer and separation phenomena

Expected impact

• Economic/Social Shorter reaction times reduction in lead time

reduction in cost Increased selectivity of reactions increase in material

yield raw material savings Improvement in separation efficiency cost reduction Miniaturization of equipment reduction in investment

cost

Overall improved resource & energy efficiency Increased sustainability

Expected impact

• Environmental Reduction in emissions & waste increase in

resource & energy efficiency via usage of alternative energy sources Reduction in manufacturing footprint &

environmental impact

• Low pressure – low-power microwave plasma reactor to study CO2 splitting and rWGS

1st generation plasma reactor (200 W, 100 mbar)

Plasma-assisted processes

2,25E+20

1,50E+20

1,0E+18

5,1E+19

1,0E+20

1,5E+20

2,0E+20

2,5E+20

0 100 200 300 400

Ele

ctro

n de

nsity

(1/m

3 )

Length Reactor (mm)

Waveguide

No Waveguide

1,35 1,42

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

0 100 200 300 400

Elec

tron

Tem

pera

ture

(eV)

Length Reactor (mm)

Waveguide

No Waveguide

• Co-axial waveguide plasma reactor to extend the plasma flame and residence time in the plasma zone

Model-based plasma reactor design

2nd generation plasma reactor

20 kWth Feed: lignin (0.5 mm particles) 40% cold gas efficiency @ 90% lignin conversion <1 mol% methane Negligible CO2 emission (plasma agent: air/N2) Scalable process (2.45, 0.92 GHz)

Initial atmospheric plasma reactor configuration Redesigned downstream reactor assembly

3rd generation plasma reactor

batch flow

high speed camera

US generator and amplifier

transducers, horns, baths, other means?

Off-line or on-line separation & analytics

(LDA, HPLC, GC)

Ultrasound-assisted processes

13

Matching work on transducers and amplifiers

Reliability tests Development of modular

design to match continuous processing

Ongoing work on US technology

14

(Source: Smart Material)

MW-assisted crystallisation

• Heat input by MW to dissolve smaller crystals more homogeneous CSD

15

(Source: Sairem )

Summary

• Plasma-, microwave- and ultrasound-based processes have been studied a lot of kinetic and process data is missing first scale-up examples ready

• Several of them currently under revision with end-users; technico-economic study ongoing

• Matching of energy supplying devices with process equipment is crucial

Appl

icat

ion

area

s

TUDO TUD

YORK SAIREM

JP

JP KUL TUD

SAIREM

AN TUDO TUD

SAIREM SM

Advanced pharmaceutical synthesis

Green fuel synthesis

Technologies

Dem

onstration

WP 1 WP 3 WP 2

WP 5

WP 4

KUL TUD

TUDO JP

SM

TUD AN

SAIREM

Data generation Mechanisms and models

Equipment design and scale up

General Work Plan

Ultra-sound

Micro-waves

Plasma

Acknowledgements EC: Carmine Marzano (PO) and Bob Valeras (PTA)

TU Delft: Andrzej Stankiewicz, Herman Kramer, Guido Sturm, Rohit Kacker, Xavier KU Leuven: Tom Van Gerven, Georgios Stefanidis, Leen Braeken, Leen Thomassen,

Jeroen Jordens, Bjorn Gielen, Jinu John, Gunjan Agrahari TU Dortmund: Andrzej Gorak, Dorota Pawlucka, Mirko Skiborowski, Philip Lutze,

Matthias Wierschem, Katrin Werth, Alexander Niesbach, Felizitas Rall, Petra Marciniak

University of York: Duncan Macquarrie, Mario de Bruyn, Vitaly Budarin Smart Material: Jan Kunzmann, Frank Wolfram Sairem: Marilena Radoiu Akzo Nobel: Tony Kiss, Riaan Schmul Janssen Pharma: Peter Van Broeck, Luc Moens, Thomas Rammeloo, Rob Geertman

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